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High-energy long-cycling all-solid-state lithium metal batteries enabled by silver–carbon composite anodes

A Publisher Correction to this article was published on 20 March 2020

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An all-solid-state battery with a lithium metal anode is a strong candidate for surpassing conventional lithium-ion battery capabilities. However, undesirable Li dendrite growth and low Coulombic efficiency impede their practical application. Here we report that a high-performance all-solid-state lithium metal battery with a sulfide electrolyte is enabled by a Ag–C composite anode with no excess Li. We show that the thin Ag–C layer can effectively regulate Li deposition, which leads to a genuinely long electrochemical cyclability. In our full-cell demonstrations, we employed a high-Ni layered oxide cathode with a high specific capacity (>210 mAh g−1) and high areal capacity (>6.8 mAh cm−2) and an argyrodite-type sulfide electrolyte. A warm isostatic pressing technique was also introduced to improve the contact between the electrode and the electrolyte. A prototype pouch cell (0.6 Ah) thus prepared exhibited a high energy density (>900 Wh l−1), stable Coulombic efficiency over 99.8% and long cycle life (1,000 times).

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Fig. 1: All-solid-state lithium metal battery.
Fig. 2: Morphology of direct Li plating on the current collector with the SSE.
Fig. 3: Stable Li plating and stripping through the Ag–C nanocomposite layer.
Fig. 4: Morphological variation of the Ag–C nanocomposite layer.
Fig. 5: Characterization of Ag and C particles in the Ag–C nanocomposite layer after cycling.
Fig. 6: Electrochemical performance of ASSB with SSEs.

Data availability

All the data generated or analysed during this study are included in this published article and its Supplementary Information files. The data that support the plots within this paper are available from the corresponding authors upon reasonable request.

Change history


  1. Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).

    Google Scholar 

  2. Janek, J. & Zeier, W. G. A solid future for battery development. Nat. Energy 1, 16141 (2016).

    Google Scholar 

  3. Kato, Y. et al. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 1, 16030 (2016).

    Google Scholar 

  4. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).

    Google Scholar 

  5. Lau, J. et al. Sulfide solid electrolytes for lithium battery applications. Adv. Energy Mater. 8, 1800933 (2018).

    Google Scholar 

  6. Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2017).

    Google Scholar 

  7. Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).

    Google Scholar 

  8. Pfenninger, R., Struzik, M., Garbayo, I., Stilp, E. & Rupp, J. L. M. A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nat. Energy 4, 475–483 (2019).

    Google Scholar 

  9. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).

    Google Scholar 

  10. Nie, K. et al. Interfaces between cathode and electrolyte in solid state lithium batteries: challenges and perspectives. Front. Chem. 6, 616 (2018).

    Google Scholar 

  11. Sakuda, A., Hayashi, A. & Tatsumisago, M. Sulfide solid electrolyte with favorable mechanical property for all-solid-state lithium battery. Sci. Rep. 3, 2261 (2013).

    Google Scholar 

  12. Ohtomo, T., Hayashi, A., Tatsumisago, M. & Kawamoto, K. Suppression of H2S gas generation from the 75Li2S·25P2S5 glass electrolyte by additives. J. Mater. Sci. 48, 4137–4142 (2013).

    Google Scholar 

  13. Zhou, L. et al. Solvent-engineered design of argyrodite Li6PS5X (X = Cl, Br, I) solid electrolytes with high ionic conductivity. ACS Energy Lett. 4, 265–270 (2019).

    Google Scholar 

  14. Wenzel, S., Sedlmaier, S. J., Dietrich, C., Zeier, W. G. & Janek, J. Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes. Solid State Ion. 318, 102–112 (2018).

    Google Scholar 

  15. Chen, B., Xu, C., Wang, H. & Zhou, J. Insights into interfacial stability of Li6PS5Cl solid electrolytes with buffer layers. Curr. Appl. Phys. 19, 149–154 (2019).

    Google Scholar 

  16. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    Google Scholar 

  17. Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).

    Google Scholar 

  18. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    Google Scholar 

  19. Ferrese, A. & Newman, J. Mechanical deformation of a lithium-metal anode due to a very stiff separator. J. Electrochem. Soc. 161, A1350–A1359 (2014).

    Google Scholar 

  20. Masias, A., Felten, N., Garcia-Mendez, R., Wolfenstine, J. & Sakamoto, J. Elastic, plastic, and creep mechanical properties of lithium metal. J. Mater. Sci. 54, 2585–2600 (2019).

    Google Scholar 

  21. Narayan, S. & Anand, L. A large deformation elastic–viscoplastic model for lithium. Extreme Mech. Lett. 24, 21–29 (2018).

    Google Scholar 

  22. Qian, J. et al. Anode-free rechargeable lithium metal batteries. Adv. Funct. Mater. 26, 7094–7102 (2016).

    Google Scholar 

  23. Genovese, M., Louli, A. J., Weber, R., Hames, S. & Dahn, J. R. Measuring the Coulombic efficiency of lithium metal cycling in anode-free lithium metal batteries. J. Electrochem. Soc. 165, A3321–A3325 (2018).

    Google Scholar 

  24. Yang, C.-P., Yin, Y.-X., Zhang, S.-F., Li, N.-W. & Guo, Y.-G. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 6, 8058 (2015).

    Google Scholar 

  25. Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).

    Google Scholar 

  26. Yan, K. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat. Energy 1, 16010 (2016).

    Google Scholar 

  27. Wang, H. et al. Wrinkled graphene cages as hosts for high-capacity Li metal anodes shown by cryogenic electron microscopy. Nano Lett. 19, 1326–1335 (2019).

    Google Scholar 

  28. Yang, C. et al. Ultrafine silver nanoparticles for seeded lithium deposition toward stable lithium metal anode. Adv. Mater. 29, 1702714 (2017).

    Google Scholar 

  29. Park, C.-M., Kim, J.-H., Kim, H. & Sohn, H.-J. Li-alloy based anode materials for Li secondary batteries. Chem. Soc. Rev. 39, 3115–3141 (2010).

    Google Scholar 

  30. Park, C.-M., Jung, H. & Sohn, H.-J. Electrochemical behaviors and reaction mechanism of nanosilver with lithium. Electrochem. Solid-State Lett. 12, A171–A175 (2009).

    Google Scholar 

  31. Feng, W., Dong, X., Li, P., Wang, Y. & Xia, Y. Interfacial modification of Li/garnet electrolyte by a lithiophilic and breathing interlayer. J. Power Sources 419, 91–98 (2019).

    Google Scholar 

  32. Pei, A., Zheng, G., Shi, F., Li, Y. & Cui, Y. Nanoscale nucleation and growth of electrodeposited lithium metal. Nano Lett. 17, 1132–1139 (2017).

    Google Scholar 

  33. Wang, M. et al. Porous carbon hosts for lithium–sulfur batteries. Chem. Eur. J. 25, 3710–3725 (2019).

    Google Scholar 

  34. Xie, J. et al. Engineering stable interfaces for three-dimensional lithium metal anodes. Sci. Adv. 4, eaat5168 (2018).

    Google Scholar 

  35. Kraft, M. A. et al. Inducing high ionic conductivity in the lithium superionic argyrodites Li6+xP1–xGexS5I for all-solid-state batteries. J. Am. Chem. Soc. 140, 16330–16339 (2018).

    Google Scholar 

  36. Kato, Y. et al. All-solid-state batteries with thick electrode configurations. J. Phys. Chem. Lett. 9, 607–613 (2018).

    Google Scholar 

  37. Koerver, R. et al. Redox-active cathode interphases in solid-state batteries. J. Mater. Chem. A 5, 22750–22760 (2017).

    Google Scholar 

  38. Koerver, R. et al. Capacity fade in solid-state batteries: interphase formation and chemomechanical processes in nickel-rich layered oxide cathodes and lithium thiophosphate solid electrolytes. Chem. Mater. 29, 5574–5582 (2017).

    Google Scholar 

  39. Xiao, Y., Miara, L. J., Wang, Y. & Ceder, G. Computational screening of cathode coatings for solid-state batteries. Joule 3, 1252–1275 (2019).

    Google Scholar 

  40. Ito, S. et al. A rocking chair type all-solid-state lithium ion battery adopting Li2O–ZrO2 coated LiNi0.8Co0.15Al0.05O2 and a sulfide based electrolyte. J. Power Sources 248, 943–950 (2014).

    Google Scholar 

  41. Stevens, D. A. & Dahn, J. R. The mechanisms of lithium and sodium insertion in carbon materials. J. Electrochem. Soc. 148, A803–A811 (2001).

    Google Scholar 

  42. Dahn, J. R., Zheng, T., Liu, Y. & Xue, J. S. Mechanisms for lithium insertion in carbonaceous materials. Science 270, 590–593 (1995).

    Google Scholar 

  43. Tachikawa, H. & Shimizu, A. Diffusion dynamics of the Li atom on amorphous carbon: a direct molecular orbital−molecular dynamics study. J. Phys. Chem. B 110, 20445–20450 (2016).

    Google Scholar 

  44. Persson, K. et al. Lithium diffusion in graphitic carbon. J. Phys. Chem. Lett. 1, 1176–1180 (2010).

    Google Scholar 

  45. Zheng, G. et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 9, 618–623 (2014).

    Google Scholar 

  46. Zhang, W. et al. (Electro)chemical expansion during cycling: monitoring the pressure changes in operating solid-state lithium batteries. J. Mater. Chem. A 5, 9929–9936 (2017).

    Google Scholar 

  47. Walther, F. et al. Visualization of the interfacial decomposition of composite cathodes in argyrodite-based all-solid-state batteries using time-of-flight secondary-ion mass spectrometry. Chem. Mater. 31, 3745–3755 (2019).

    Google Scholar 

  48. Hippauf, F. et al. Overcoming binder limitations of sheet-type solid-state cathodes using a solvent-free dry-film approach. Energy Storage Mater. 21, 390–398 (2019).

    Google Scholar 

  49. Suzuki, N., Yashiro, N., Yamada, T. & Aihara, Y. All-solid-state secondary battery and method of charging the same. US patent no. US20190157723A1.

  50. Suzuki, N., Yashiro, N. & Aihara, Y. Li electroplating/stripping on the metal substrate coated with carbon black. In. Proc. 235th ECS Meeting abstr. 163 (ECS, 2019).

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This work was supported by funds from Samsung Electronics Co. Ltd.

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Authors and Affiliations



D.I., Y.A. and I.T.H. proposed and supervised the research. N.S., N.Y. and Y.A. proposed the metal–carbon composite concept. Y.-G.L., T. Sugimoto, S.R., N.S. and N.Y. optimized the Ag–C composite anode as well as the current collectors for the anode to achieve the best cycle performance. J.H.K., S.F. and T. Shiratsuchi optimized the effect of external pressure on the battery performance. R.O. developed and optimized the SSE. S.F. and T. Shiratsuchi designed and fabricated the high-Ni-based NMC cathode and prototype ASSB as well as the stacked cell (<5 Ah). S.F., R.O. and T. Shiratsuchi carried out the safety tests for LIB and ASSB. C.J. and Y.-G.L. conducted the SEM, Raman and XRD characterizations. D.-S.K. performed the TEM characterization to monitor the morphological changes in the Ag and C particles. S.R. and Y.-G.L. performed the X-ray CT analysis. Y.-G.L., T. Sugimoto, J.H.K., S.R., Y.P., S.F., N.S., N.Y., R.O., T. Shiratsuchi and T.W. performed the electrochemical characterizations. Y.-G.L., D.I., Y.A., S.F. and T.W. analysed the data and wrote the manuscript. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yong-Gun Lee, Yuichi Aihara or Dongmin Im.

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Competing interests

All the authors are employed at Samsung Electronics Co. Ltd.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Notes 1–4 and Tables 1–3.

Supplementary Video 1a

Heating test (LIB)

Supplementary Video 1b

Heating test (ASSB)

Supplementary Video 2

Oil bath test

Supplementary Video 3

Cutting test

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Lee, YG., Fujiki, S., Jung, C. et al. High-energy long-cycling all-solid-state lithium metal batteries enabled by silver–carbon composite anodes. Nat Energy 5, 299–308 (2020).

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